Methine dyes and a process for the preparation thereof



UNITED 'M HIN Grafton H. Keyes,

,No Drawing.

Patented Jan. 9, 1940 STAT DYES ,AND A, PROCESS FOR THE PREPARATION THEREOF Rochester, N; :Y.,'assignor-to I PATENT OFFICE Eastman'Kodak Company, Rochester, N. Y., a corporation of New Jersey r v Serial No. 146,425.

Original application June 4,1937.

Divided and this applica tion-Augusta, 1938, Serial No. 227,853

. Claims. (01. 260-240 'lhisinventionrelates'to dyes and to aprocess for the preparation thereof.

Certain. dyes are known ample, certain to alter the sensitivity of photographic silver halide emulsions. 'Forex .dyes of the cyanlne class have .been found to alter the sensitivity of photographic emulsions.

U. S. Patent No. 2,078,233,

Dyes of the merocyanine class (see dated April 27, 1937) havebeen found to sensitize photographic emulsions. More recently, certain dyes of the hemioxonol class have been found to alter the sensitivity of [photographic emulsions (see a copending application of .Lesl

ie, G. S.','.Brooker, Serial No.

101,105, niecseptemperis, 1936). However, not

all dyes alter the sensitivity sions. .In order for a graphic silver halideemulsion,

of photographic emu}- dye, to sensitize a photoit must not only ,be adsorbed bythe silver halide in the emulsion,

but mustbe so adsorbed that of energy-between the dye/and the silverhalide obtains. -It is, of course,-

whethernor not a dye willbe halide and whether or a proper exchange impossibleto forecast not the 'dyewill be adsorbed in amanner which permits the proper exchange of energy between the dye and the silver halide.

I have now found dyes.

entirely new class of I have further found that these new dyes sensitize photographic silverhalide emulsions in a new and useful manner.

See my cop ndins application Serial No. 146,425, filed June 4,1937, of which the instant application is a division.

' An object of my present I A further object, is to is to provide new dyes.

invention, therefore,

provide, new photographic, sensitizing dyes. I A

still further object. is to preparation of my new dyes.

appear hereinafter. 3

' The dyes of my inventioncan, for convenience,

provides. process for Other objects'will be illustrated by the following general formula:

. h D .E v I I J-N-( .)..=c-( :=.i

' wherein A represents a oxygengroup, such as oxygen or sulfur, L representsa inethenyl group, n 'represents a positive odd-integer not greater than five, J

atom of the divalent non-metallic D and E each represent an organic (carbon-containing) group or D and E together represent the non-metallic. atoms necessary to complete a cyclic organic nucleus.

"J represents hydrogen or an aliphatic group while Q represents an aliphatic group, orJ and Q togeth metallic atoms necessary er represent the nonto complete a cyclic methyl, ethyl, adsorbed on asilver wherein A, L', n,J and have the vaiues'indicated above under Formula I, and 2 represents the. non-metallic, atoms necessary to complete a heterocyclic nucleus, e. g'., a five-membered or sixrmembered heterocyciic nucleus.

More particularly, in Formulas I and II, J and Q can each represent an 'alkyl group,v such as n-butyl, allyl, benzyl, p -hydro'xyethyl, furylmethyl" (furfuryl) or the like and J and Q together can represent'the non-metallic atoms necessary to complete an organiccyclic basic nucleus, such as a piperidine, a tetra-hydroquinoline, a N-alkylpiperazine, a piperazine, a morpholine or like basic nucleus. Z can represent the non-metallic atoms necessary to complete a flve-membered heterocyclic nucleus, such I as a thiazolone nucleus, for example, a 2,4(3,5)

thiazoiedione nucleus, such as 2,4(3,5) -thiazoledi one, 3-a1kyl-2,4( 3,5) -thiazoledione, 3-phenyl- 2,4 (3,5) -thiazoledione v or 3-naphthyl-2,4 (3,5) thiazoledione nuclei, 9; 2-tliio-,2,4 (3,5) -thiazoledione (a rhodanine) nucleus, such as 3-aikyl-2- thio-2,4(3,5)'-thiazoledione (S-alkylrhodanine) 3- phenyl-2-thio-2,4(3,5) -thiazoledione (3-phenylrhodanine, 3-na'phthyl-2-thio-2A(3,5) -thiazoledione (ii-naphthylrhodaninel nuclei or 3-( 1- benzothiazyl)"-2-thio-2,4(3,5) thiazoledi'one -(3- (1 hen'zothiazyl) 'rh'odanine) nuclei, a 2,4-dithio-' 2,4(3,5)-thiazoledione (4 thiorhodanine) nucleus,

' such as 2,4-dithio 2,4(3,5) thiazoledione or its 3- 'alkyl, 3-phenyl or S' naphthyl derivatives, a 2- Y alkylmercepici(5) thiazolone nucleus. such as 2- nucleus, for example, a 2-thio-2,4(3,5) -oxazoledione nucleus; such as a 3alkyl-2-thio-2,4(3,5)

'oxa zoledione nucleus; an imida'zolone nucleus, for

example a 2,4(3,5)-imidazo1edione nucleus, such as 2,4(3,5) -imidazoledicne (hydantoin) or its 3- ethy1mercapto-4(5)'-thiazolone, a 'thiazolidone, nucleus',such as '4-thiazolidone or its S-alkyl 3- phenyl or 3 -na-phthyl derivatives a Z-alkylphenylamino-4(5)-thiazolone nucleus or a'2-diphenylamino-4(5)-thiazolone nucleus; "an oxazolone I alkyl, 3-phenyl or B-naphthyl derivatives as well as its 1,3-dialkyl, 1-alkyl-3-phenyl, 1-alky1-3- naphthyl, 1,3-diphenyl, etc. derivatives, 2. 2-thio- 2,4(3,5)-imidazoledione nucleus, such as 2-thio- 2,4(3,5)-imidazoledione (Z-thiohydantoin) or its 3-alkyl, 3-phenyl or 3-naphthyl derivatives as well as its 1,3-dialkyl, l-alkyl-B-phenyl, l-allgvl- 3-naphthyl, 1,3-diphenyl, etc. derivatives, a 4- thio-2,4(3,5)-imidazoledione nucleus, such as 4- thio-2,4(3,5) -imidazoledione (4-thiohydantoin) or its 3-alkyl, B-phenyl or B-naphthylderivatives as well as its 1,3-dialkyl, 1-alkyl-3-phenyl, 1- alkyl-3-naphthyl, 1,3-diphenyl .etc. derivatives, 2. 2-alkylmercapto-5(4)-imidazo1one, such as 2- propylmercapto-5(4)-imidazolone; a thionaphthenone nucleus, such as 2-(l)-thionaphthenone or 1(2)-thionaphthenone, a pyrazolone nucleus, for example a fi thiopyrazolone, such as l-phenyl- 3-methyl-5-thiopyrazolone; an oxindole nucleus, such as 2,3-dihydro-3-ketoindole, and like fivemembered heterocyclic nuclei. The dyes containing a five membered heterocyclic nuclei containing both a nuclear nitrogen and a nuclear sulfur atom give rise to emulsions of particular utility. The dyes containing a five-membered heterocyclic nuclei containing a nuclear nitrogen atom and a nuclear thiocarbonyl group, I have found, are also very well adapted to the production of useful photographic emulsions. A can also represent the non-metallic atoms necessary to complete a six-membered heterocyolic nucleus, such as a 2,4,6-triketohexahydropyrimidine nucleus, for example barbituric acid or Z-thiobarbituric acid as well as theirl-alkyl or 1,3-dialkyl derivatives; a 3,4-dihydro-2(1)-quinolone .nucleus, such as 3,4-dihydro-2(l) -quinolone (dihydrocarbostyril; a 3,4-dihydro-2(1) -quinoxalone nucleus,

- /Z\ R-N-(L),-=bd=A wherein A represents a divalent non-metallic atom, such as oxygen or sulfur, L represents a III methenyl group, n represents a positive odd integer not greater than five, R represents an acyl group, such as acetyl, propionyl or benzoyl, R represents an aryl group, such as a phenyl, a diphenyl, a xylyl or a naphthyl group, i. e. an aryl group of twelve or less nuclear carbon atoms, for example, and Z represents the non-metallic atoms necessary to complete a hterocyclic nucleus, 'suchas the five-membered or six-membered heterocyclic nucleus illustrated above in connection with Formula II. Compounds represented by Formula III are described irr'the copending application of Leslie G. S. Brooker, Se-

rial No. 101,105, filed September 16, 1936. Certain compounds (where n equals one) represented by Formula III have also been described by Dains et a1. See for example J. Am. Chem. Soc. 31, 1148 (1909); 35, 959-0913); 38, 1841 (1916); 40, 562 (1918); 44, 2310 (1922) and Ber. 35, 2496 (1902).

As shown in the above referred to application of Leslie G. S. Brooker compounds of Formula III can be prepared by first reacting a compound of the following formula:

wherein L represents a methenyl group, n represents a positive odd integer not greater than five, and R and R" represent aryl groups, such as phenyl, xylyl, diphenyl or naphthyl, with a heterocyclic compound of the following formula:

wherein A represents a divalent non-metallic atom, such as oxygen or sulfur, and Z represents the non-metallic atoms necessary to complete a heterocyclic nucleus, such as the five-membered or six-membered heterocyclic nuclei pointed out above under Formula II. Some of the compounds represented by Formula IV are basic and accordingly form salts with acids such as hydrochloric, sulfuric and the like. These salt forms can be used as well to react with the compounds of Formula V. Examples of compounds of Formula'IV and their salts which can be advantageously employed are: diphenylformamidine, fl-anilinoacrolein anil and its hydrochloride,- p-anilino-abromo-acrolein anil, p-anilino-a-chloro-acrolein anil and their hydrochlorides, glutaconic-aldehyde dianilide hydrochloride, a-(p-naphthylimiIIO-e- (flnaphthylamino) arr-methyl -a,'ypentadiene hydrochloride (see Konig, Journal fur praktische Chemie, vol. 69 page 136), etc. Compounds such as diphenyl formamidine are advantageously reacted with compounds of Formula V, in the presence of a petroleum fraction, e. g., kerosene, as shown in the examples below. Compounds suchas p-anilinoacrolein anil or glutaconic aldehyde or their hydrochlorides or other salts canbe reacted with compounds of Formula V by heating the substances together, advantageously in the presence of a strong tertiary organic base.

The reaction products of compounds of Formula IV and compounds of Formula V can be advantageously converted into their acylated derivatives, i. e., the compounds of Formula III, by

action of compounds of Formula IV with compounds of Formula V, as illustrated below. Other methods of forming the acylated compounds of Formula III, can be employed such as treatment with acid chlorides instead of acid anhydrides. I have found the acetylated compounds of Formula III very suitable for preparing my new dyes.

Basic non-aromatic primary or secondary amines which can be used to react with compoundsof Formula III are, for example, aliphatic amines for instance, monoalkylamines, such as methylamine, ethylamine, n-butylamine, sec-butylamine, isopropylamine, n-decylamines, allylamine, cyclohexylamine, furylmethyl'amine, tetrahydrofurylmethyl amine, benzylamine, 13 hydroxyethylamine, or the like or dialkyl-amines, such as dimethylamine, diethyl-amine. di-n-butyl-amine, di-B-hydroxyethylamine, diallylamine my process.

or the like,or heterocyclic basic secondary amines for instance five-membered heterocyclic secnd-- ary amines, such as pyrrolidenes, or the like, or six-membered heterocyclic basic secondary amines, such as piperidine, piperazine, N-alkylpiperazines, 1,2,3,4-tetrahydroquinoline, morpho lines or the like. Pyrrol cannotbe employed in The basicnon-aromaticprimary or secondary amines are advantageously reacted with the,

compounds of. Formula 111 in the presence of a diluent, such as a lower aliphatic alcohol, i'. e., one of four carbon atoms or less. However, the diluent is not essential. If used, the diluent is advantageously substantially anhydrous. Other ethylidene dichloride, ethyldioxane can be used. inert toward the dyes and is advantageously chosen so that the formed dye will separate therefrom at least upon cooling the reaction mixture. Heat accelerates the formation of my new dyes. The basic non-aromatic primary or secondary amine-is advantageously employed in molecular excess, from 1.5 to 3 mo lecular proportions (mol.) per molecular'propor tion of compound of Formula III is.suitable. With a molecular ratio of 1:1 the yield of my new dyes is generally lower'thanwhen an excess of the non-aromatic amine is employed.

While the process of preparing my new dyes diluents such as ene dichloride or diluent should be is subject to variation particularly as respects.

the nature and quantities of reactants, the nature and'quantity of temperatures, the following examples will serve to illustrate the mode of preparation of the dyes of Formula II where n represents one. These examples are not intended to limit myv invention.

7 EXAMPLE 1 5- (1 -piperidyl) -methylene.-3phenglrhodanine Ha Ha s N-C H; mo N-oH=c 0.9 g. (1 mol.) of 5-acetanilidomethylene-S- phenylrhodanine, 0.6 g. (3 mol.) of piperidine .and 30 cc. of absolute ethyl alcohol were heated under reflux for about 30 minutes. .The dye separated from the cooled reaction mixture and after two recrystallizations from methyl alcoholformed yellow needles melting at 286-288 C.

The 5acetanilidomethylene-B-phenylrhodanine used in the above example was prepared'by heating under reflux for, about 15 minutes 1.55 g. (l mol.) of 5-anilinomethylene-3-phenylrhodanine, 15 cc. of acetic anhydride and 0.5 g. (1 mol.) of triethylamine. The crude product was recrystallized twice from methyl alcohol and was obtained as minute yellow crystals 'melt'ing at 194-198 C. with decomposition. The 5-anilinodiluent employed andthe I prepared by methylene-3-phenylrhodanine was prepared according to the method of Dains, Kansas Univ. ScienceBull. 15, 265 (1924) by heating together equimolecular proportions of 3-phenylrhodanine and diphenylformamidine in kerosene (about 300 cc. per gram molecular proportioniof 3-phenyl- -,rhodanine is suitable) at about 120 C. The reaction product separated and was'washed with methyl alcohol. ItQwas'recrystallized'trom glacial acetic acid.

Ex'suru: 2

r 3-eihyl-5 (1 -piperidj l) -methylenerhodanine 9.'75 g. (1 mol.) of S-acetanilidomethylene-3- ethylrhodanine, 9.6 g (3 mol.) of piperidine and cc. of absolute ethyl alcohol were heated under reflux for about minutes. The dye separated from the cooled reaction mixture, It was twice recrystallized from methyl alcohol and was obtained as pale yellow needles melting at, 150.5- l52.5 C. Itsmethylalcohol solution was pale' yellow. i

The 5-acetanilidomethylene-3-ethylrhodanine employed above was prepared by refluxing; for

- about 10 minutes, 1.3 g. (1 mol.) of 5-anilinomethylene-S-ethylrhodanine with l0cc. of acetic anhydride and 0.5 or triethylamine'. The crude product was twice recrystallized ,from methyl alcohol and obtained as pale yellow crystals melting at 128-130 C. .JThe ,5-anilinomethylene-3- ethylrhodanine was prepared by heating together equimolecular proportions of 3-ethylrhodanine and ,{diphenylformamidine according to the method of Dains (seeEx. l). 1

' Exmrta 3 5- (4-morpholyl) -mc thylewe-3-ethyL-2-thio- 2,4 3,5) orazoledione 9:1 g. (1 may of 5-acetanilldomethylene-3- ethyl-2-thio-2,4(3,5) -oxazoledione, 0.7 g. (3 mol.) morpholine and 10 cc. absolute ethyl alcohol were heated under reflux for about 30 minutes. The dye separated from the cooled reaction mixture. It was recrystallized from 'waterand was obtained as colorless crystals melting at 164-6 '03. with decomposition. It gave a colorless aqueous solution. 0

The 5-acetanilidomethylene-3-ethyl-2A(3,5) oxazoledione employed in the above example was beating 8.7 g. (1 mol.) of 5-anilinomethylene-3-ethyl-2'A(3,5) oxazoledione with 30 'cc. of acetic anhydride and 3.7 g. (1 mol.). of triethylamine at 100 C. for about 10 minutes. The crude product separated from the cooled reaction mixture. It was'twice recrystallized from methyl alcohol and obtained as nearly colorless crystals, melting at 158-l60 C. The 5-anilinomethylene- 3-ethyl-2,4(3,5) oxazoledione was obtained according to the method of Dains as illustrated in Example 1 by heating equimolecular proportions of diphenylformamidine and 3-ethyl-2,4(3,5)- oxazoledione together in kerosene.

In the above examples, the piperidine and morpholine can be replaced with other basic primary or secondary non-aromatic amines such as pointed out above in connection with reaction with compounds of Formula III. Likewise the 3-ethylrhodanine and 3-phenylrhodanine can be replaced by other heterocyclic compounds containing a nuclear methylene group adjacent to a nuclear carbonyl group, such as correspond to the five-membered and six-membered heterocyclic nuclei pointed out under Formula II above, for example.

The following examples will serve to illustrate the formation, of the dyes of Formula II, where n representsthree. These examples are not intended to limit my invention.

Exmu: 3-ethyl-5- 1 -piperidyl) allulidene] -rhodanine H3 H1 l- 8 \NCIH mc N-cH=cH-cH=c ll, 1t.

0.8 g. (1 mol.) of -acetanilidoallylidene)- 3-ethylrhodanine, 0.6 g. (3 mol) of piperidine and cc. of alsolute ethyl alcohol were heated under reflux for about 30 minutes. The dye separated from the cooled reaction mixture. It was twice recrystallized from methyl alcohol and obtained as light brownish crystals havinga bluish reflux and melting at 187-9 C. with decomposition. Its methyl alcoholic solution was deep yellow.

The 5 (-y-acetanilidoallylidene) -8-ethylrhodanine employed above was prepared byrefluxing 3.2 g. (1 mol.) of 3-ethylrhodanine, 5.2 g (1 mol.) of fi-anilinoacrolein anil hydrochloride and 30 cc. of acetic anhydride for about one hour. The reaction product separated from the cooled reaction mixture and after two recrystallizations from acetic acid was obtained as pale yellow crystals melting at 225.5226.5 C.

EXAMPLE 5 3-ethz/l-5- [-y-(4-m0rphol1 Dall1 lidenelrhodanine 0.8 g. (1 mol.) of 5-('y-acetanilidoallylidene)- 3-ethylrhodanine, 0.7 g. (3 mol.) of morpholine and 15 cc. of absolute ethyl alcohol were heated under reflux for about 30 minutes. The dye separated from the cooled reaction mixture and after two recrystallizations from methyl alcohol was obtained as minute orange red crystals, melting at 225.5-227.5 C. with decomposition. Its methyl alcoholic solution was yellow.

Exam: 6 v 5-( diethylamin0allyidene) -3-ethylrhodam'ne CIH CIHI

0.8 g. (1 mol.) of 5-(' -acetanilidoallylidene) B-ethylrhodanine, 0,6 g. (3 mol.) of diethylamine and 15 cc. of absolute ethyl alcohol were heated under reflux for about 30 minutes; The dye separated from the cooled reaction mixture and after two recrystallizations from methyl alcohol formed amber needles with a blue reflux, melting at 133-l35 C. with decomposition. Its methyl alcoholic solution was "new;

EXAMPLE 7 Z-diphenylamino-S- [-y -(1-piperidyl) -allylidenel 4(5) -thiazolone N C Hs): Ha Ha 1.0 g. (1 mol.) of 5-(v-acetanilidoallylidene)- 2-diphenylamino-4(5) -thiazolone, 0.6 g. (3 mol.) of piperidine and cc. of absolute ethyl alcohol were heated under reflux for about minutes.

The dye separated from the cooled reaction mixture. After two recrystallizations from ethyl al- .cohol, the dye was obtained as brownish yellow EXAMPLE 8 3-ethyl-5- [7- (piperz'dyl) allylidene] -2-thio- 2,4( 3,5) -o:zazoledione 1.6 g. (1 mol.) of 5-('y-acetanilidoallylidene)- 3-ethyl-2-thio-2,4(3,5)-oxazoledione, 1.2 g. (3 mol.) of piperidine and 10 cc. absolute ethyl alcohol were heated under reflux for about 30 minutes. The dye separated from the cooled reaction mixture. After two recrystallizations from 70% aqueous ethyl alcohol, the dye was obtained as orange yellow crystals melting at 1205-1235 with decomposition. The ethyl alcoholic solution of the dye was yellow.

The 5-(' -acetanilidoallylidene 3 ethyl- 2 thio-2,4(3,5)-oxazoledione employed above was prepared by refluxing 2.9 g. (1 mol.) of 3-ethyl-2- thio-2,4(3,5) -oxazoledione, 5.2 g. (1 mol.) of anilinoacrolein anil hydrochloride, 30 cc. of ab- I, to

auaooe solute ethyl alcohol and 2.0 g. (2 mol.) of triathylamine for about 30 minutes. The crude product, 5-( -anllinoallylldene)- 3 ethyl 2 thio 2.4(3,5)-oxazoledione, separatedir'om the cooled reaction mixture. 5.8 g. (1 mol.) ofthis crude product, 30 cc. of acetic anhydride and 2.0 g. (1 'mol.) of triethylamine were heated to refluxing for about 5 minutes.

9 recrystallizations from methyl alcohol was obtained as minute greenish yellow crystals melting at 247-249" C. with decomposition.

ene] -5-pyraz0lone zyl-3-methyl-5- pyrazolone employed above was prepared by refluxing 4.6 g. (1 mol.) oil-benzo thiazyl-3-methyl-5-pyrazolone, 5.2. g. (1 111.01.). of

-anilinoacro1ein anil hydrochloride and 2 5.00

of acetic anhydride for about .10 minutes. The

, product separated from the cooled reaction mixture and was used without recrystallization.

Exlmru: 10

Z-thiohydantoin m thyl-1-phenyz-5-[ -u-piperiduzr au uaenei 55 1 g. (lmoL) or 5-(v-acetanilidoallylidene)-3 ethyl-1-phenyl-2-thiohydantoin, 0.6 g. (3 .mol.).

of piprldine and cc. of absolute ethyl alcohol.-

Thed'yefl v g cooled reactionv mixture. It V 1 g were refluxed'for about minutes). 4 separated fromathe was recrystallized twice from methyl alcohol and obtained as reddish crystals melting at 1895191 C. with decomposition. 7'

The 5-( -acetanilidoallylidene) 3, ethyl- 1 4 phenyl-Z-thiohydantoin, ing 4.4 g. (1 mol.) of 3-ethyl-1-phenyl-2-thiohy :dantoin, 5 .g'.&"(=1 moi.) :ofimahilinoacrolein anil;

hydrochloride, 30 cc. of absolute ethyl alcohol and 2.0 g. (1 mol.) of triethylamine were refluxed for about 30 minutes. The crude product separated from the cooled reaction mixture and was used without recrystallization. 1.75 g. (1 moi).

of this crude product, and 0.5 g. (1 mol.) of at C. for about 15 minutes.

10 cc. of acetic anhydride triethylamine were heated The product The product separated g from the. cooled reaction mixture and after two alcohol and obtained as orange 1.0 g. (1 mol.) of 4-('y-acetanilidoaliylidene) and 10 cc. absolute ethyl cooled reaction mixture.

about 30 minutes.

the cooled reaction with decomposition.

any of the basis primary or aromatic amines pointed out above in connec-' tion with reaction with compounds of Formula.

"-: preparationof equals ave; ,These examples are not intended to limit my invention. 1 r

wasprepared by refluxseparated from the cooled reaction mixture and Exam 11 0.85 g. (1-mol.)' or 4-(r -acetanilidoallylidene)- .mclting at 184-180- C.

3-methyl-1-phenyl-5-pyrazolone; 0.6 g. (3 mol.)

Y of piperidine and 10 cc.'of absolute ethylalcohol H g for about 30 minutes. The dye separated from the cooled reaction mix- It was twice. recrystallized from methyl" were heated under reflux ture.

Y crystals melting at 187-189 C. Its'metl'iyl alcoholic solution was yellow. Y

phenyl-S-pyrazolone employed above was prepared by refiuxing 3.5g. (1 mol.) of 3-methyl-1- phenyl -5-pyrazolone, 5 g.

hydride and 2g. ,(1 mol.) oftriethylamine for The product separated from crystallizations from methyl alcohol'was obtained as flakyorange crystals melting at 212-214" C.

In the above eight examples,

secondary: non- III. Likewise the 3-ethyl-2-'thlo- 2,4(3,5) ,-oxazoledione, l-benzothiazyl- 3 methyl 5 pyrazolone, 3-ethyll- -phenyl-2-thiohydantoin,- S-methyl 1- .-phenyl-5-pyrazolone, 3-ethylrhodanine. 2-diphenylamino-elw) -thia'zolone, 4-thlorhodanine and barbituric acid can be replaced with any heterocyclic compound containingv a nuclear methylene 1 group adjacent to a nuclear carbonyl group, such to the flve-membered and sixmembered heterocyclic nuclei pointed out above as correspond under Formula II, for example. The dyes derived frompiperidine are especially well adapted to the manufacture pi 'photographic emulsions,

1 have found...

The following 7 the dyes of Formula; II where n Exciter: 12

0.9 g. 1 m1.) of s-(s-acetanilido-A entam 8. (3 "mol.) of

The dye separated from the cooled reaction mixture and wasrecrystallizedftwicefrom 05% mixture and after two i'eg the plperldin morpholine and diethylamine can bereplaced by examples serve'to illustrate the g (1 mol.) of p-anilino- I acrolein anil hydrochloride, 20 cc. of acetic an'-.

g; (1 mol.) of triethylamine for about three minutes. The product separated from the cooled reaction mixture and without recrystallization was heated to boiling with 50 cc. of acetic anhydride. The product separated from the cooled reactionmixture and was used without recrystallization.

Exsuru: 13

3 ethyl 5 [5 (4 morpholyl) A f -pentadienylidenel-rhodanine v i $1 o-o s N-c,m o N-oH=oH-oH=oH-o11=o-- =o 0.9 g. (1 mol.) of -(5-acetanilldo-N- -pentadienylidene-3-ethylrhodanine, 0.7 g. (3 mol.) of morpholine and cc. of absolute ethyl alcohol were heated under reflux for about minutes. The dye separated from the cooled reaction mixture. It was recrystallized three times from ethyl alcohol and obtained as dark blue crystals melting at 179482" C. with decomposition. Its ethyl alcoholic solution is bluish red.

Exsmmr: 14

5 (5 diethylamino A pentadienylidene) 3-eth1 Zrh0danine 0.9 g. (1 mol.) of 5-(fi-acetanllido-A -penta dienylidene) -3-ethylrhodanine, 0.9 g. (3 mol.) of diethylamine and 10 cc. of absolute ethyl alcohol were heated under reflux for about 30 minutes. The dye separated from the cooled reaction mixture and after several recrystallizations from ethyl alcohol was obtained as steel blue needles melting at 112.5-114.5 C. with decomposition. Its ethyl alcoholic solution was bluish red.

In theabove three examples, the piperidine, diethylamine and morpholine can be replaced with any of the basic non-aromatic primary or secondary amines pointed out in the above in connection with reaction with compounds of Formula III above. The 3-ethylrhodanine can be replaced by any heterocyclic compound containing a nuclear methylene group adjacent to a nuclear carbonyl group, such as correspond to the heterocyclic nuclei pointed out under FormulaIIabove. I

To prepare dyes of Formula II where Z represents the non-metallic atoms necessary to complete a 2alkylm ercapto-4(5)-imidaz01one nu cleus, dyes of Formula II where Z represents the non-metallic atoms necessary to complete a rhodanine or a hydantoin (free from substituents lowing:

in the 1- position) nucleus can be treated with alkylatlng agents. For example, dyes such as 5 (1 piperidyl) methylenerhodanine, 5 ['y- 1- piperidyl)allylidenel rhodanine, 5 ['y (4 morpholyl) allylidene] -rhodanlne, 5- [5- l-plperidyl) -A -pentadienylidene] -rhodanine, 5-(1-piperidyl) methyienehydantoln, 5 diethylaminomethylene-2-thiohydantoin, 5-[v-(1-piperidy1) a1- lylidene] 2 thiohydantoin and 5 [5 (4 morpholyl A pentadienylidene] 2 thiohydantoin can be alkylated by suspending one molecular proportion in methyl .alcohol, adding about 1.2 moi. of powdered alkali, e. g. potassium hydroxide and then adding about 1.2 mol. of alkylating agent, e, 'g. dialkyl sulfates, or advantageously alkyl-p-toluene-sulfonates. The reaction mixture is refluxed for about 30 minutes ordinarily, though longer time may be required in some instances. The allq'lated dye separates from the chilled reaction mixture.

All of the dyes, illustrations of which have been given above, are particularly useful in manufacturing photographic emulsions servingto alter the sensitivity thereof; these dyes are also useful inmanuiacturing light filters and in the dyeing of textiles, particularly textiles made from cellulose acetate yarn.

Related to the dyes illustrated above and coming under Formula I above are dyes which can be represented bythe following formula:

VI D E b nana amino or naphthyl amino, or an alkyl group, such as methyl, ethyl, or the like.

These new related dyes can be prepared in a manner similar to that illustrated above, 1. e., by reacting a basic non-aromatic primary or secondary amine with a compound of the following formula:

VIII D E wherein A, n, R and R have the values pointed out under Formula III above while D and E have the values pointed out under Formula VI above. The basic primary or secondary non-aromatic amines which can be reacted with compounds of Formula VII are the same as those pointed out above in connection with reaction with compounds of FormulaIII. Thefcompounds of Formula VII are first obtained by methods similar to those illustrated above for preparingcompounds of Formula III. Thus, for example, diphenylformamidine (in kerosene) or s-anilinoacrolein anil hydrochloride (in acetic anhydride) or glut-aconic aldehyde dianilide hydrochloride (in acetic anhydride) can be condensed with the folbenzoylacetonitrile, naphthoylacetonitrile, cyanoacetanilide, malonic acid, diethylmalonate, acetoacetic ester, acetylacetone, benzoylacetone, or the like. The resulting compound is then converted to its acylated form if it is not already in that form. The acylation can be effected as illustrated in the above examples.

a- (1 -piperidyl) -allylidene l -be1iz0ylacet0'- 0.8 g. (1 mol.) of a-('y acetanilido-allylidene) benzoylacetonitrile, 0.6g. (3"mol.) of piperidinex;

and 15 cc. of absolute ethyl alcohol were heated; under refiuxfor about 30 minutes. The dye separated from the cooled reaction mixture and after two recrystallizations from methyl alcohol. was obtained as orange-yellow needles melting Its methyl at ISO-162 C.'with decomposition. alcoholic solution was-yellow; I The oz- -acetanilido-allylidene) -benzoylacetd;

nitrile used in the above example was preparedf by first refluxing for about 30 minutes 1.45 g. (1

B-anilinoacrolein anil hydrochloride, 20' cc. of

absolute ethyl alcohol'a'nci 1.0 g. (1 mol.) of tri ethylamine. The product separated from. the cooled reaction mixture and was used in the crude form to prepare the acetanilido derivative as fol lows: 5.5 g. (1 mol.) of the crude product, 40 cc. of acetic anhydride and 2.0 g. of triethylamine were heatedat 100 C. for about 10 minutesl:

The crude product separated from the cooled reaction mixture and'after two recrystallizatioris from methyl alcohol was obtained as yellow needles melting at 208-210 C.' withdecomposition!v These new dyes of my invention represented" by Formula VIv are useful in preparing photographic emulsions, in preparing light"filters and in the dyeing of textiles made from cellulose acetate yarn. v,

Dyes similar in structureto the preferred group of the dyes of my invention (represented by" Formula II above) can be prepared from carbocyclic compounds containing a nuclear methylene group adjacent to a nuclear carbonyl group, e. g., from 1,3-cyclohexadione orfrom indandione" or the like. The method of preparation issimilar to that illustratedabove, viz., first condensing the indandione or similar carbocyclic compound with a compound of Formula III followed by treating the resulting condensation product with a primary or secondary non-aromatic amine asf The'dyes from these carboillustrated above. cyclic compounds, such as indandione or 'l,'3-

cyclohexadione, are of lesser utility in manufacturing photographic emulsions; but are suited for the preparation of light filters and can be ftextiles madefrom cellulose" 1 used for dyemg O wherein represents a divalent non-metallic acetate yarn.

From the breadth'of description given through out these specifications; it is" clear that dyes con"- taining simple substituents on the nuclei or methenyl (CH) chains are a part of my inven-- tion. Still further examples of the preparation of my new dyes could be given, but the foregoing will be sufiicient to teach-those skilled i n the art the manner of obtaining my new dyes.

My new dyes can be called hemioxonol dyes. Those containing one methenyl group (where n gelatino-silyerhalide emulsions. newhemioxonol dyes'fca'n be employed in emul- 'sions'in 'whichfthe carrier is other than gelatin, "for example'fa resinous substanceor cellulosic formula: 1 i

in Formulas I and II: represents onelcanbe' called simple hemioxonol dyes? those containing a-chainof three'methenyl groups :(where n represents three) can be called hemicarboxonol dyes, and those containing a chain of five methen'yl groups" ,(where ,{n representative) can be called hemidicarb'oxonol dyes."

Myv new hemioxonoldyes give rise to photographic emulsionspossessing' novel sensitivity when incorporatedatherein. My invention is particularly directed tothe customarily employed However, my

derivative 'which hassubstantially no deleterious effect onthelight-sensitive materials. As silver halide emulsions, we include such emulsions as are commonly employed in the art, for example,

silver chloride-or silver bromide emulsions which can containother'saltswhich may be light-sensitive. Bywayof illustration, the herein-described sensitized photographic emulsions wereprepared employing ordinary: gelatin'o silver-chloride and gelatino silver bromide emulsions. My new simple hemioxon'olndyes' (where n .represents one) are advantageously employed with silver chloride emulsions.- -My*newhemicarboxonol dyes, are likewiseladvantageously employed in manufactoring-"sensitized "silver chloride emulsions.

What"I" claim"as my "invention-and desire to be securedibyllletters"Patent-of'the United States isf v .1. A." dye characterized" by the following wherein represents: a divalent anon'ernetallic "atom selected mm the group consisting vo1,oxygen and. sulfur h represents a methenyl group,

n representsfa. positive odd integer. not 1 greater than fiv J, represents a substltuent; selected from the group consisting of hydrogen and alkyl groups when, Q represents an alkyl group and vJ and Q together represent. .the non-.rnetallic atoms complete an :organic .h'eterocyclicj nucleus selected from thegroup cons'isting of fiveemembered andf six-membered'organic heterocyclic nuclei.

2'. A 'dyeff.characteriaed, by ,the following atom sel'ected from the group consisting of oxygen andsulfur; L represents a methenyl group, n represents a positive odd integer not greater than five, J'and'Q togetherrep'resent the nonmetallicatoms'necessaryto complete a six-mem bered organic cyclic bas'icfnucleus and Z renresents the non'fniet'allic atoms necessary to'com} plete aifivemembered heterocyclic nucleus contraining a nuclear nitrogen and 'a nuclear sulfur,

atom.

'3. dye having the following formula: I

5. A dye having the following formula:

6. A process for preparing a dye comprising reacting an amine selected from the group consisting of primary and secondary non-aromatic basic-'amines-other than pyrrol with a compound of the following formula:

wherein A represents a divalent non-metallic atom of the oxygen group, L represents a methenyl group, n represents a positive odd integer, D and E each represent organic groups, and E and D together represent the non-metallic atoms necessary to complete a cyclic organic nucleus,

R represents an acyl group and R represents an aryl group.

'7. A process for preparing a dye comprising reacting an amine selected from the group consisting of primary and secondary non-aromatic basic amines other than pyrrol with a compound of the following formula:

wherein L represents a methenyl group, n represents a positive odd integer not greater than five,

D and E each represent organic groups, and D and E together represent the non-metallic atoms necessary to complete a cyclic organic nucleus, R

represents an acyl group and R represents an aryl group.

9. A process for preparing a dye comprising reacting an amine selected from the group consisting of six-membered organic heterocyclic basic amines containing one --NH- group with a compound of the following formula:

RITIOH=CHOH=ICC'=A wherein A represents a divalent non-metallic atom selected from the group consisting of oxygen and sulfur, R represents an acetylgroup, R represents a phenyl group and Z represents the non-metallic atoms necessary to complete a heterocyclic nucleus selected from the group con- ;sisting of flve-membered and six-membered heterocyclic nuclei.

, 10. A process for preparing a dye comprising 1 reacting from about'one' and one-half molecular proportions to'about three molecular proportions of an amine selected from the group consisting of six-membered organic heterocyciic basic amines containing one --NH- group with a compound of the following formula:

,z, I RlTI -CH=CH-CH=b-d=0 1i wherein R represents an acetyl group, R represome a phenyl group and Z represents the nonmetallic atoms necessary to complete a heteroof five-membered and six-membered hetero" cyclic nuclei. I

12. A process for preparing a dye comprising reacting from about one and one-half to about three molecular proportions of piperidine with a compound of the following formula:

V, g z

, wherein R represents an ac'etyl group, R represents a phenyl group and Z represents the nonmetailic atoms necessary to complete a 2-thio- 2,4(3,5)-thiazoledione nucleus.

13. A process for preparing a dye comprising reacting from about one and one-half to about three molecular proportions of piperidine with a compound of the following formula:

wherein R represents an acetylgroup, R reprecyclic nucleus selected from the group consisting 14. A process for preparing a dye comprising reacting from about one and one-half to about three molecular proportions of plperldine with a compound of the following formula:

I v\ R--N-OH=CE-.-OH==?J-I-C"=O wherein It represents an acetyl group, R represents a phenyl group and Z represents the nonmetallic atoms necessary to complete a 2-thiohydantoin nucleus.

15. A dye having the following formula:

Iz\\ r-N-oH=on-om-b-d-o wherein J and Q together represent the nonmetallic atoms necessary to complete a sixmembered organic basic cyclic nucleus and Z represents the non-metallic atoms necessary to complete a 2-thio-2,4(3,5)-thiazoledione nucleus.

16. A dye having the following formula:

IZR IN-OH=-0H-OH=bd-0 represent the nonwherein J and Q- together to complete a sixmetalllc atoms necessary membered organic basic cyclic nucleus and. Z

represents the non-metallic atoms necessary to complete a 2-thiohydantoin nucleus. 1'7. A dye having the following formula:

' is I wherein J and Q together represent the non-5 wherein Z represents wherein wherein Z represents metallic atoms necessary to complete a sixmembered basic vcycllc organic nucleus and Z represents the non-metallic atoms necessary to complete a 3-allryl-2-thio-2,4(3,5)-oxazoledlone nucleus.

18. A dye having the following formula:

the non-metallic atoms necessary to' complete a 2-thio-2,4(3,5)-thlazoledione nucleus. 1 v

19.- A dye having the following formula:

Z represents the non-metallic atoms necessary to complete a 2-thiohydantoin nucleus.

20. .A dye having the following formula:

oaer'rou a. me. 

